Amido peroxycarboxylic acids for bleaching

ABSTRACT

A bleaching composition and a method of using the same. The composition comprising: 
     (i) from about 0.1 to about 50% by weight of an amido peroxyacid having the structure: ##STR1## wherein, R, R 1 , R 2 , R 3 , n, n&#39;, m, m&#39;, and M are as defined in the specification; and 
     (ii) from about 0.5 to about 50% by weight of a surfactant.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention concerns novel amido peroxycarboxylic acids and their useas bleaches, especially in the cleaning of fabrics.

2. The Related Art

Organic peroxyacids have long been known for their excellent bleachingactivity. For instance, U.S. Pat. No. 4,642,198 (Humphreys et al)describes a variety of water-insoluble organic peroxyacids intended forsuspension in an aqueous, low pH liquid. The preferred peroxy materialis 1,12-diperoxydodecanedioic acid (DPDA). Surfactants, both anionic andnonionic, are utilized as suspending agents. When formulated with 10%surfactant, DPDA exhibits good stability under storage conditions. Whenthe surfactant level of the formulation is increased to 22%, a leveltypical for a heavy-duty laundry detergent, the half-life of the DPDAdecreases dramatically. For example, U.S. Pat. No. 4,992,194 (Liberti etal) reports that at 40° C. the half-life of DPDA is only 1 to 2weeks ina pH 4-4.5 heavy-duty laundry liquid.

Another effective peracid is 4,4'-sulfonylbisperoxybenzoic acid (SBPB)reported in EP 0 267 175 (Dyroff et al) as possessing superior storagestability. U.S. Pat. No. 4,822,510 (Madison et al) demonstrates theincreased stability of SBPB over DPDA in an aqueous liquid bleachingcomposition.

U.S. Pat. No. 4,634,551 (Burns et al) and U.S. Pat. No. 4,686,063(Burns) describe peroxyacids having polar amide links along ahydrophobic backbone. These substances are stabilized with an exothermcontrol agent selected from boric acid and urea. Described in detail area variety of n-acyl aminoperoxyacids and alkylamino oxoperoxy acids. Allof the reported substances are mono-percarboxylic acids. A relatedpatent, EP 0 349 220 (P&G), suggests use of a phosphate buffer solutionand a pH between about 3.5 and 6 for improving storage stability ofamido peroxyacids.

U.S. Pat. No. 5,061,807 (Gethoffer et al) and U.S. Pat. No. 5,132,431(Fuchs et al) describe a series of imido peroxyacids, chief among whichis N-phthaloylamino peroxycaproic acid (PAP). Suspension ofimidoperoxycarboxylic acids in an aqueous system is achieved through useof sodium alkylbenzene sulfonate as reported in EP 0 435 379 (AkzoN.V.). Related technology in EP 0 347 724 (Ausimont) disclosesheterocyclic peracids such as N-acyl-piperidine percarboxylic acids. WO90/14336 (Interox) discloses 6,6'-terephthal-di(amidoperoxyhexanoic)acid and 6,6'-fumaryl bis(amidoperoxyhexanoic) acid.

Although many of the amido and imido peroxyacids have a quite dramaticbleaching activity, their stability, especially under alkalineconditions, in surfactant solutions remains a considerable problem.Clearly there is a need for new peracids specifically designed forheavy-duty laundry liquids. These materials also need to be physicallystable in terms of thermal and shock sensitivity and in terms of storagestability

In view of the problems of the art, it is an object of the presentinvention to provide new peroxycarboxylic acids with effective bleachactivity.

Another object of the present invention is to provide peroxycarboxylicacids with superior storage stability.

Still another object of the present invention is to provide newperoxycarboxylic acids that, in addition to excellent activity, are alsocharacterized by good storage stability when suspended in an aqueousmedium but nevertheless can rapidly be dissolved in an alkaline washmedium.

A still further object of the present invention is to provide a methodof bleaching fabrics in a fully-formulated, heavy-duty laundry detergentcomposition through the use of new peroxycarboxylic acids.

These and other objects of the present invention will become morereadily apparent through consideration of the following summary,detailed description and examples.

SUMMARY OF THE INVENTION

An amido peroxyacid compound is provided having the formula: ##STR2##wherein:

R is selected from the group consisting of C₁ -C₁₂ alkylene, C₅ -C₁₂cycloalkylene, C₆ -C₁₂ arylene and radical combinations thereof;

R¹ and R² are independently selected from the group consisting of H, C₁-C₁₆ alkyl and C₆ -C₁₂ aryl radicals and a radical that can form a C₃-C₁₂ ring together with R³ and both nitrogens;

R³ is selected from the group consisting of C₁ -C₁₂ alkylene, C₅ -C₁₂cycloalkylene and C₆ -C₁₂ arylene radicals;

n and n' each are an integer chosen such that the sum thereof is 1;

m and m' each are an integer chosen such that the sum thereof is 1; and

M is selected from the group consisting of H, alkali metal, alkalineearth metal, ammonium, alkanolammonium cations and radicals andcombinations thereof. Furthermore, there is provided a bleachingcomposition comprising:

(i) an effective amount for bleaching of an amido organic peroxyacidhaving the general structure (I); and

(ii) from about 0.5 to about 50% of a surfactant.

A method is also provided for bleaching a substrate, especially laundryand dishes, comprising contacting the substrate with an amido peroxyacidof the general structure (I).

DETAILED DESCRIPTION

Now a new series of amido percarboxylic acids has been found having thestructural formula: ##STR3## wherein:

R is selected from the group consisting of C₁ -C₁₂ alkylene, C₅ 14 C₁₂cycloalkylene, C₆ 14 C₁₂ arylene and radical combinations thereof;

R¹ and R² are independently selected from the group consisting of H, C₁-C₁₆ alkyl and C₆ -C₁₂ aryl radicals and a radical that can form a C₃-C₁₂ ring together with R³ and both nitrogens;

R³ is selected from the group consisting of C₁ 14 C₁₂ alkylene, C₅ -C₁₂cycloalkylene and C₆ -C₁₂ arylene radicals;

n and n' each are an integer chosen such that the sum thereof is 1;

m and m' each are an integer chosen such that the sum thereof is 1; and

M is selected from the group consisting of H, alkali metal, alkalineearth metal, ammonium, alkanolammonium cations and radicals andcombinations thereof.

Within the general formula there are two subcategories of structureswhich are particularly advantageous. These substructures are as follows:##STR4## wherein:

R¹, R² and R³ are defined in the same manner as that for formula (I) andz is an integer from 1 to 20.

Particularly preferred compounds representing substructure (II) are thefollowing: ##STR5## A particularly preferred compound representative ofsubstructure (IV) is as follows: ##STR6## Synthesis of compoundsaccording to the present invention can be accomplished through thecondensation of difunctional amines and acids to form diacids ordiesters linked by diamide moieties. Using this chemistry, there havebeen condensed a variety of diamines with two equivalents of themono-acid chloride mono-ester of either terephthalic acid or adipic acidto provide some novel diamide diesters. Similarly, 4-aminobenzoic acidhas been condensed with diacid chlorides to yield diamide diacids. TableI lists some of the combinations tested.

                  TABLE I                                                         ______________________________________                                        Condensation Combinations Yielding Diamide Diesters                           Acid Derivative   Amine Derivative                                            ______________________________________                                        4-carbomethoxybenzoyl chloride                                                                  ethylenediamine                                              "                butanediamine                                                "                piperazine                                                   "                trans-1,4-diaminocyclohexane                                 "                1,4-phenylenediamine                                         "                1,2-phenylenediamine                                        carboethoxyadipoyl chloride                                                                     1,4-phenylenediamine                                         "                ethylenediamine                                             succinoyl chloride                                                                              4-aminobenzoic acid                                         terephthaloyl chloride                                                                          "                                                           ______________________________________                                    

Condensation of the diamines with the acid chlorides can be achieved byadding a toluene solution of the acid chloride dropwise to an aqueoussolution of the diamine and excess potassium carbonate at roomtemperature. The resulting diamide precipitates from the biphasicreaction medium.

For purposes of this invention, the imido structure is not oneencompassed herein.

A second method may be employed for those systems having specialsensitivity to water. An anhydrous preparation is conducted where theamine and the acid chloride are dissolved in chloroform. Either pyridineor triethylamine can be utilized as a base for removing hydrogenchloride. This procedure is especially useful for compounds such asSDPCA and 1,2-PCBPD. For many of the amides, more than one method cansuccessfully be employed in their preparation.

Conversion of the diamide diesters or diacids to the mono-peroxyacidsmay be accomplished using a standard procedure outlined by Swern et aldescribed in Org. Synth., (1963), 43, 93-96 and in U.S. Pat. No.3,180,886. The diesters or diacids, which usually are completely solublein methanesulfonic acid, may be treated with 1 to 4.5 molar equivalentsof 70 or 90% hydrogen peroxide at room temperature for 3 to 5 hours.

When incorporated into a cleaning composition, the amido peroxyacids ofthe present invention will range in concentration from about 1 to about40%, preferably from about 1.5 to about 15%, optimally between about 2and about 5% by weight.

A detergent formulation containing a peroxyacid bleach system accordingto the invention will usually also contain surfactants and detergencybuilders. When in liquid form, the surfactants serve not only to cleanbut importantly function as a structuring system to suspend thewater-insoluble amido peroxyacids in water or any other solvent carrier.For heavy-duty laundry liquids, it is also important to include a pHadjusting system and advantageously a deflocculating polymer.

The surface-active material may be naturally derived, such as soap or asynthetic material selected from anionic, nonionic, amphoteric,zwitterionic, cationic actives and mixtures thereof. Many suitableactives are commercially available and are fully described in theliterature, for example in "Surface Active Agents and Detergents",Volumes I and II, by Schwartz, Perry and Berch. The total level of thesurface-active material may range up to 50% by weight, preferably beingfrom about 1% to about 40% by weight of the composition, most preferably4 to 25%.

Synthetic anionic surface-actives are usually water-soluble alkali metalsalts of organic sulfates and sulfonates having alkyl radicalscontaining from about 8 to about 22 carbon atoms, the term alkyl beingused to include the alkyl portion of higher aryl radicals.

Examples of suitable synthetic anionic detergent compounds are sodiumand ammonium alkyl sulfates, especially those obtained by sulfatinghigher (C₈ -C₁₈) alcohols produced for example from tallow or coconutoil; sodium and ammonium alkyl (C₉ -C₂₀) benzene sulfonates,particularly sodium linear secondary alkyl (C₁₀ -C₁₅) benzenesulfonates; sodium alkyl glyceryl ether sulfates, especially thoseethers of the higher alcohols derived from tallow coconut oil andsynthetic alcohols derived from petroleum; sodium coconut oil fatty acidmonoglyceride sulfates and sulfonates; sodium and ammonium salts ofsulfuric acid esters of higher (C₉ -C₁₈) fatty alcohol-alkylene oxide,particularly ethylene oxide reaction products; the reaction products offatty acids such as coconut fatty acids esterified with isethionic acidand neutralized with sodium hydroxide; sodium and ammonium salts offatty acid amides of methyl taurine; alkane monosulfonates such as thosederived by reacting alpha-olefins (C₈ -C₂₀) with sodium bisulfite andthose derived by reacting paraffins with SO₂ and Cl₂ and thenhydrolyzing with a base to produce a random sulfonate; sodium andammonium C₇ -C₁₂ dialkyl sulfosuccinates; and olefinic sulfonates, whichterm is used to describe the material made by reacting olefins,particularly C₁₀ -C₂₀ alpha-olefins, with SO₃ and then neutralizing andhydrolyzing the reaction product. The preferred anionic detergentcompounds are sodium (C₁₁ -C₁₅) alkylbenzene sulfonates; sodium (C₁₆-C₁₈) alkyl sulfates and sodium (C₁₆ -C₁₈)alkyl ether sulfates.

Examples of suitable nonionic surface-active compounds which may be usedpreferably together with the anionic surface-active compounds, includein particular, the reaction products of alkylene oxides, usuallyethylene oxide, with alkyl (C₆ -C₂₂) phenols, generally 2-25 EO, i.e.2-25 units of ethylene oxide per molecule; the condensation products ofaliphatic (C₈ -C₁₈) primary or secondary linear or branched alcoholswith ethylene oxide, generally 2-30 EO, and products made bycondensation of ethylene oxide with the reaction products of propyleneoxide and ethylene diamine. Other so-called nonionic surface-activesinclude alkyl polyglycosides, polyhydroxy fatty acid amides (e.g. C₁₂-C₁₈ N-methyl glucamide), long chain tertiary amine oxides, long chaintertiary phosphine oxides and dialkyl sulphoxides.

Amounts of amphoteric or zwitterionic surface-active compounds can alsobe used in the compositions of the invention but this is not normallydesired owing to their relatively high cost. If any amphoteric orzwitterionic detergent compounds are used, it is generally in smallamounts in compositions based on the much more commonly used syntheticanionic and nonionic actives.

The detergent compositions of the invention will normally also contain adetergency builder. Builder materials may be selected from (1) calciumsequestrant materials, (2) preciptating materials, (3) calciumion-exchange materials and (4) mixtures thereof.

In particular, the compositions of the invention may contain any one ofthe organic or inorganic builder materials, such as sodium or potassiumtripolyphosphate, sodium or potassium pyrophosphate, sodium or potassiumorthophosphate, sodium carbonate, the sodium salt of nitrilotriaceticacid, sodium citrate, carboxymethylmalonate, carboxymethyloxysuccinate,tartrate mono- and di-succinates, oxydisuccinate, crystalline oramorphous aluminosilicates and mixtures thereof.

Polycarboxylic homo- and copolymers may also be included as builders andto function as powder structurants or processing aids. Particularlypreferred are polyacrylic acid (available under the trademark Acrysolfrom the Rohm and Haas Company) and acrylic-maleic acid copolymers(available under the trademark Sokalan from the BASF Corporation) andalkali metal or other salts thereof.

These builder materials may be present at a level of, for example, from1 to 80% by weight, preferably from 10 to 60% by weight.

Upon dispersal in a wash water, the initial amount of peroxyacid shouldrange in amount to yield anywhere from about 0.05 to about 250 ppmactive oxygen per liter of water, preferably between about 1 to 50 ppm.Surfactant should be present in the wash water from about 0.05 to 1.0grams per liter, preferably from 0.15 to 0.20 grams per liter. Whenpresent, the builder amount will range from about 0. 1 to 3.0 grams perliter.

For heavy-duty laundry detergent liquids, it is advantageous to employ asystem to adjust pH, known as a "pH jump system". It is well-known thatorganic peroxyacid bleaches are most stable at low pH (3-6), whereasthey are most effective as bleaches in moderately alkaline pH (7-9)solution. To achieve the required pH regimes, a pH jump system may beemployed to keep the pH of the product low for peracid stability yetallow it to become moderately high in a wash water for bleaching anddetergency efficacy. One such system is borax.10H₂ O/polyol. Borate ionand certain cis-1,2-polyols complex when concentrated to cause areduction in pH. Upon dilution, the complex dissociates, liberating freeborate to raise the pH. Examples of polyols which exhibit thiscomplexing mechanism with borate include catechol, galactitol, fructose,sorbitol and pinacol. For economic reasons, sorbitol is the preferredpolyol. To achieve the desired concentrate pH of less than 6, ratiosgreater than about 1:1 of polyol to borax are usually required.Therefore, the preferred ratio of polyol to borax should range anywherefrom about 1:1 to about 10: 1. Borate compounds such as boric acid,boric oxide, borax with sodium ortho- or pyroborate may also be suitableas the borate component.

Another advantageous component in the heavy-duty liquid laundrydetergent compositions of this invention is a deflocculating polymer.Copolymers of hydrophilic and hydrophobic monomers usually are employedto form the deflocculating agent. Suitable polymers are obtained bycopolymerizing maleic anhydride, acrylic or methacrylic acid or otherhydrophilic monomers such as ethylene or styrene sulfonates and the likewith similar monomers that have been functionalized with hydrophobicgroups. These include the amides, esters, ethers of fatty alcohol orfatty alcohol ethoxylates. In addition to the fatty alcohols andethoxylates, other hydrophobic groups, such as olefins or alkylarylradicals, may be used. What is essential is that the copolymer haveacceptable oxidation stability and that the copolymer have hydrophobicgroups that interact with the lameliar droplets and hydrophilic groupsof the structured liquid to prevent flocculation of these droplets andthereby, prevent physical instability and product separation. Inpractice, a copolymer of acrylic acid and lauryl methacrylate (M. W.3800) has been found to be effective at levels of 0.5 to 1%. Thesematerials are more fully described in U.S. Pat. No. 4,992,194 (Liberatiet al) herein incorporated by reference.

Apart from the components already mentioned, the detergent compositionsof the invention can contain any of the conventional additives in theamounts in which such materials are normally employed in detergentcompositions. Examples of these additives include lather boosters suchas alkanolamides, particularly the monoethanolamides derived frompalmkernel fatty acids and coconut fatty acids, lather depressants suchas alkyl phosphates and silicones, antiredeposition agents such assodium carboxymethylcellulose and alkyl or substituted alkylcelluloseethers, other stabilizers such as ethylene diamine tetraacetic acid,fabric softening agents, inorganic salts such as sodium sulfate andusually present in very small amounts, fluorescent whitening agents,perfumes, enzymes such as proteases, cellulases, lipases and amylases,germicides and colorants.

The amido peroxyacids described herein are useful in a variety ofcleaning products. These include laundry detergents, laundry bleaches,hard surface cleaners, toilet bowl cleaners, automatic dishwashingcompositions and even denture cleaners. Peroxyacids of the presentinvention can be introduced in a variety of product forms includingpowders, on sheets or other substrates, in pouches, in tablets or innonaqueous liquids such as liquid nonionic detergents.

The following examples will more fully illustrate the embodiments ofthis invention. All parts, percentages and proportions referred toherein and in the appended claims are by weight unless otherwiseillustrated.

EXAMPLE 1 Monomethyl monopotassium terephthalate

A solution of 87.5% KOH (143 g, 2.24 moles) in 870 mL of methanol wasadded to ground dimethylterephthalate (434 g, 2.24 moles) in 2,420mltoluene at room temperature over a period of 45 minutes. The reactionmixture was heated at 65° C. for three hours with stirring and was thenallowed to cool to room temperature. The solids were filtered, washedwith 3500ml of warm toluene, and dried to yield 464.08 grams (95% yield)of a white solid. IR (nujol) 1735, 1600, 1550, 1410, 1290, 730 cm⁻¹.

N,N'-Di (4-carbomethoxybenzoyl)piperazine

Monomethyl monopotassium terephthalate (175.8 g, 0.8056 mol) wassuspended in toluene (2000 mL) in a 5 L, 3-necked flask equipped with anoverhead stirrer, a condenser, and an addition funnel. Thionyl chloride(58.76 mL, 0.8056 mol) was added dropwise to the rapidly stirredsuspension and the mixture was heated at 67° C. for three hours. Afterstirring overnight at rt, the reaction was filtered on a Buchner funnelthrough a bed of celite and the flitrate containing4-carbomethoxybenzoyl chloride was retained. At this point the acidchloride can be isolated by addition of an equal volume of diethylether, filtration of the potassium chloride by-product and removal ofthe solvent in vacuo. For most procedures the toluene solution is useddirectly.

In a 5 L Morton flask, potassium carbonate (266.2 g, 1.61 mol) andpiperazine (34.69 g, 0.4027 mol) were dissolved in 1000 mL of water. Thetoluene solution of 4-carbomethoxybenzoyl chloride was added dropwisewhile the internal reaction temperature was maintained at 25° C. Themixture was stirred overnight, filtered and washed with toluene, water,1N HCl and water to provide 127 g (77%) ofN,N'-di(4-carbomethoxybenzoyl)piperazine as a white solid. mp. 234°-237°C.; IR (nujol) 1730, 1630, 1610, 1510, 1290, 1260, 1010, 730 cm⁻¹.

¹ H NMR (200MHz, CDCl₃ /CD₃ COCD₃) δ7.48-8.11 (8H, m), 3.93 (6H, s),3.81 (4H, br s), 3.56 (4H, br s); ¹³ C NMR (ODCl₃ /CD₃ COCD₃)δ169.51,166.05, 139.19, 131.50, 129.89, 126.98, 52.31, 43.80, 41.10; IR(nujol) 2920, 2840, 1720, 1620, 1605, 1455, 1430, 1370, 1360, 1275,1260, 1100, 1000 cm⁻¹ ; low res. MS (Cl, isobutane) 411 (MH+).

(N-(4-Carboxybenzoyl)-N'(4-percarboxybenzoyl)piperazine (CBPBPIP)

The ester obtained above is hydrolyzed to the corresponding dicarboxylicacid by known methods. (Green, T. W.; "Protective Groups in OrganicSynthesis", John Wiley & sons: New York, 1981, pp. 158-159) Theresulting N,N'-di(4-carboxybenzoyl)piperazine (0.0099 mol) is dissolvedin methanesulfonic acid (14 mL) and treated with hydrogen peroxide (1.69mL of a 70% solution, 0.0446 mol) at 0° C. The mixture is stirred atroom temperature for 3 to 5 hours, then poured onto ice-water. Thesolids are collected on a Buchner funnel, washed with water until the pHis 5, then allowed to air dry overnight.

EXAMPLE 2 N,N'-Di(4-Carbomethoxybenzoyl) ethylenediamine

Prepared using the procedure described forN,N'-di(carbomethoxybenzoyl)piperazine and substituting ethylenediamine(26.9 mL, 0.4028 mol) for piperazine and using 400 mL of water insteadof 1000 mL. Yield 88.6 g (57%); mp. 297-299° C.; ¹ H NMR (200 MHz,DMSO-d₆) δ8.82 (2 H, br s), 8.06-7.94 (8 H, m), 3.88 (6 H, s), 3.47 (4H, s); IR (nujol) 3300, 1730, 1640, 1550 cm⁻¹.

N-(4-Carboxybenzoyl)-N'-(4-Percarboxybenzoyl)ethylenediamine (CBPBED)

The title peracid is obtained fromN,N'-di(4-carbomethoxybenzoyl)ethylenediamine using the proceduredescribed for CBPBPIP.

EXAMPLE 3 N,N'-Di(4-carbomethoxybenzoyl)-1,4-phenylenediamine

4-Carbomethoxybenzoyl chloride (9.32 g, 0.046 mol) in chloroform (95 mL)was added to 1,4-phenylenediamine (2.59 g, 0.023 mol) in triethylamine(4.81 mL, 0.035 mol) and chloroform (250 mL) at 4° C. The reaction wasallowed to warm to room temperature overnight. The chloroform wasremoved in vacuo. The solid was poured onto cold 5% HCl, filtered andwashed with dilute HCl. Recrystallization from DMF yielded 6.16 g (62%)of a pale yellow powder; mp>345° C. ¹ H NMR (DMSO-d₆) δ8.06 (8H, s),7.74 (4H, s), 3.88 (6H, s); ¹³ C NMR (H₂ SO₄ /CD₃ COCD₃) (dec. to acid)δ205, 196, 169.77, 167.10, 132.56, 130.95, 128.16, 127.79, 127.03,122.85, 119.82, 52.02; IR (nujol) 3330, 2900, 2840, 1720, 1640, 1550,1455, 1410, 1375, 1280, 1190, 1110 cm⁻¹ ; low res. MS(Cl, isobutane) 433(MH+), 271,257, 223.

N-(4-carboxybenzoyl)-N'-(4-percarboxybenzoyl)phenylenediamine (CBPBPD)

The title peracid is obtained fromN,N'-di(4-carbomethoxybenzoyl)phenylenediamine using the proceduredescribed for CBPBPIP.

EXAMPLE 4 N,N'-Di (4-carbomethoxybenzoyl)-1,4-diaminocyclohexane

4-Carbomethoxybenzoyl chloride (9.057 g, 0.0456 tool) was dissolved inchloroform (180 mL) in a 500 mL 3-necked flask equipped with amechanical stirrer and an addition funnel. To this solution was addedtrans-1,4-diaminocyclohexane (2.60 g, 0.0228 mol), triethylamine (7.5mL, 0.0535 mol) and chloroform (80 mL) at 0° C. over a period of 30minutes. The reaction was stirred for 2.5 hours and the product filteredfrom the chloroform. The wet solid was washed with 10% HCl and saturatedaqueous NaCl. The product was dissolved in concentrated sulfuric acid at0° C. and then crashed out from ice water to give a white powder inabout 80% yield; m.p. >350° C. ¹ H NMR (200 MHz, D₂ SO₄) δ8.30-7.94 (8H,m), 4.27-4.37 (8H, 2.34-1.80 (8H, br m), ¹³ C NMR (200 MHz, H₂ SO₄ /CD₃COCD₃) δ170.92, 132.32, 129.92, 129.25, 127.61, 55.04, 51.83, 24.07; IR(nujol) 3295, 2920, 2850, 1720, 1630, 1530, 1460, 1375, 1285 cm⁻¹.

N-4-(Carboxybenzoyl)-N'-(4-percarboxybenzoyl)- 1,4-diaminocyclohexane(CBPBHEX)

The title peracid is obtained fromN,N'-di(4-carboxybenzoyl)-1,4-diaminocyclohexane using the proceduredescribed for CBPBPIP.

EXAMPLE 5 Carboethoxyadipoyl Chloride

Adipic acid monoethyl ester (25.63 g, 0.147 mol) was combined withthionyl chloride (34.98 g, 0.293 mol) in a round-bottomed flask equippedwith a condenser and heated at 37° C. for 3 hours. The condenser wasreplaced by a modified still head and excess thionyl chloride removed at5mm Hg. The product (26.84 g, 95%) was distilled as a clear liquid (59°C./about 0.1 mm Hg). IR 3550, 3420, 2950, 2910, 2840, 1785, 1715, 1455,1360, 1230, 1170, 1140, 1080, 1010, 940 cm⁻¹.

N,N'-Di(carboethoxyadipoyl)-1,4-phenylenediamine

Carboethoxyadipoyl chloride (13.74 g, 0.071 mol) in chloroform (40 mL)was added to 1,4-phenylenediamine (3.89 g, 0.036 mol) in chloroform (330mL) and triethylamine (7.53 mL, 0.054 mol) at 4° C. The reaction mediumwas allowed to warm to room temperature over the course of 5 hours.Recrystallization from ethyl acetate gave 6.30 g (42%) of a white fluffysolid; m.p. 156°-160° C. ¹ H NMR (DMSO-d₆) δ9.81 (2H, s, NH), 7.49 (4H,s), 4.04 (4H, q), 1.57 (8H, m), 2.34 (8H, m), 1.18 (6H, t); ¹³ C NMRδ173.65, 171.25, 134.38, 120.74, 60.39, 36.90, 33.98, 25.01, 24.42,14.23; IR (nujol) 3290, 2920, 2840, 1720, 1645, 1540, 1455, 1370, 1290,1255, 1170 cm¹ ; low res MS(CI, isobutane) 421 (MH+).

N-Carboxyadipoyl-N'-(percarboxyadipoyl)phenylenediamine (CAPAPD)

The title peracid is obtained fromN,N'-di(carboethoxyadipoyl)-1,4-phenylenediamine and 2 equivalents ofhydrogen peroxide using the procedure described for CBPBPIP.

EXAMPLE 6 N,N'-Di(4-carbomethoxybenzoyl)-1,4-butanediamine

4-Carbomethoxybenzoyl chloride (19.07 g, 0.096 mol) was dissolved intoluene (380 mL) in a 3-necked, 1000 mL round-bottomed flask equippedwith mechanical stirrer, thermometer, and addition funnel. A solution of1,4-butanediamine in water (80 mL) was added dropwise over a period of40 minutes while the temperature of the reaction mixture was maintainedat 25° C. by a water bath. A white solid formed immediately and thereaction mixture stirred for an additional 2 hours. The solid wascollected on a frit and washed with toluene, water, 5% HCl, and water.Recrystallization from DMF gave white crystals which were dried in avacuum oven at 60° C.; yield 17.91 g (90%); m.p. 260°-261° C. ¹ H NMR(200 MHz, DMSO-d₆) δ8.70 (2H, m), 8.05-7.93 (8H, m) 3.88 (6H, s) 3.34(4H, s), 1.58 (4H, s); IR (nujol) 3300, 1720, 1625, 1530, 1275, 1105,860, 730 cm⁻¹ ; low res. MS (Cl, isobutane) 413 (MH+); ¹³ C NMR (75 MHz,DMSO-d₆) δ166.9, 165.7, 165.4, 165.2, 138.7, 131.6, 129.0, 127.5, 127.2,52.3, 26.5.

N-(4-Carboxybenzoyl)-N'-(4-percarboxybenzoyl)-1,4-butanediamine (CBPBBD)

The title peracid is obtained fromN,N'-Di(4-carbomethoxybenzoyl)-l,4-butanediamine using the proceduredescribed for CBPBPIP.

EXAMPLE 7 N,N-Di(4-carbomethoxybenzoyl)-1,2-phenylenediamine

4-Carbomethoxybenzoyl chloride (18.5 g, 0.093 mol) was dissolved inchloroform (100 mL) under nitrogen and cooled to 0° C. A solution of1,2-phenylenediamine (5.00 g, 0.046 mol) and triethylamine (12.8 mL,0.092 mol) in chloroform (350 mL) was added dropwise. After 16 hours atroom temperature, triethylammonium chloride was removed by filtration ona frit containing filter paper. The organic layer was washed with cold5% HCl (3×200 mL), saturated NaCl solution (2×150 mL), and dried overmagnesium sulfate. The product was isolated by removal of chloroformunder reduced pressure. Recrystallization from ethanol yielded 12.19 g(61%) of a white powder; m.p. 211°-216° C. ¹ H NMR (200 MHz, DMSO-d₆)δ10.24 (2H, s), 8.09-8.07 (8H, 2s), 7.69 (2H, s), 7.33 (2H, s),3.90-3.88 (6H, 2s); ¹³ C NMR (50 MHz, DMSO-d₆) δ165.29, 164.37, 138.13,131.81,130.94, 128.94, 127.69, 125.79, 125.79, 125.42, 52.08; IR(nujol)3380, 3280, 1720, 1645, 1540, 1290, 1275, 1100 cm⁻¹ ; low res. MS(Cl, isobutane) 433 (MH+) 271, 165.

N-(4-Carboxybenzoyl)-N'-(4-percarboxybenzoyl)-1,2-phenylenediamine(CBPBPD)

The title peracid is obtained fromN,N'-Di(4-carbomethoxybenzoyl)1,2-phenylenediamine using the proceduredescribed for CBPBPIP.

EXAMPLE 8 N,N'-Succinoyl-di(4-carbomethoxy)aniline

Succinyl chloride was distilled under reduced pressure prior to use. Toa 1000 mL round-bottomed flask under nitrogen, methyl-4-aminobenzoate(20 g, 0.132 mol). pyridine (10.7 mL, 0.133 mol), and chloroform (250mL) were combined and cooled to 0° C. A chloroform solution of succinoylchloride (7.5 mL, 0.068 mol) was added dropwise. A lavender precipitatewas observed upon addition. After 2 hours at room temperature theproduct was filtered on a frit, washed with 5% HCl (2×400 mL), then withwater (600 mL) and then allowed to air dry on the frit. The product wasrecrystallized from DMF and dried in a vacuum oven at 60° C. to afford16.09 g (62%) of white crystals; m.p. 284°-285° C. ¹ H NMR (200 MHz,DMSO-d₆) δ10.42 (2H, s), 7.96-7.74 (SH, s), 3.85 (6H, s), 2.75 (4H, s);IR (nujol) 3340, 3320, 1710, 1690, 1675, 1610, 1595, 1530, 1295, 1270,1175, 1160, 1105, 770 cm⁻¹ ; low res. MS (Cl, isobutane) 385 (MH+), 234,152; ¹³ C NMR (75 MHz, DMSO-d₆) δ170.9, 165.7, 143.6, 130.2, 123.6,118.2, 51.7, 31.0.

N,N'-Succinoyl-(4-carboxy)aniline-(4-percarboxy)aniline (SCAPA)

The title peracid is obtained fromN,N'-succinoyl-di(4-carbomethoxy)aniline using the procedure describedfor CBPBPIP.

EXAMPLE 9 N,N'-Di(carboethoxy adipoyl)ethylenediamine

Ethylenediamine (1.17 g, 0.0195 mol) in water (5 mL) was added dropwiseto a solution of carboethoxyadipoyl chloride (2.5 g, 0.013 mol) intoluene (36 mL) at room temperature. After stirring for an additional2.5 hours, the white solid was filtered, washed with toluene, water,0.1N HCl and water and dried in a vacuum oven at 63° C. In an attempt toeliminate an impurity evident in the IR spectrum (3080 cm⁻¹), thematerial was taken up in toluene, the insolubles removed by filtration,and the toluene removed in vacuo to yield a white powder (0.31 g, 13%);m.p. 117°-120° C. (white residue remained after most melted). ¹ H NMR(200 MHz, DMSO-d₆) δ7.83 (2H, br s), 4.05 (4H, q) 3.37 (H₂ O), 3.07 (5H,br s), 2.28-2.02 (10H, br s), 1.49 (9H, br s), 1.18 (6H, t); relative tothe ethoxy protons, the integration of peaks at 3.07 and 1.49 is high byone proton each, and at 2.28-2.02 by two protons; IR (nujol) 3300, 3080,2920, 2850, 1725, 1640, 1550, 1460, 1375, 1270, 1245, 1180, 730 cm⁻.

Since the toluene purification did not eliminate the unidentifiedimpurity, the method described for the preparation ofN,N'-(4-carbomethoxybenzoyl)piperazine was used. Carboethoxyadipoylchloride (1.0 g, 0.0052 mol) in chloroform (12 mL) was added dropwise toa solution of ethylenediamine (0.16 g, 0.0026 mol), triethylamine (0.54mL, 0.0039 mol), and chloroform (5 mL) was recrystallized from tolueneto give 0.20 g (21%) of a white powder which still contained theimpurity by IR and NMR; m.p. 120°-122° C. Recrystallization from ethylacetate also did not eliminate the impurity. ¹³ C NMR (200 MHz, CDCl₃/CD₃ COCD₃) δ207.44, 173.87, 60.38, 40.07, 36.08, 33.90, 25.12, 24.39,14.33, 14.25; low res. MS(Cl, isobutane) 373 (MH+).

N-(Carboxyadipoyl)-N'-(percarboxyadipoyl)ethylenediamine

The title peracid is obtained fromN,N'-di(carboethoxyadipoyl)ethylenediamine using the procedure describedfor CBPBPIP.

EXAMPLE 10 N,N'-Di(4-carboxyaniline)terephthalate

4-Aminobenzoic acid (2.1 eq. 14.11 g, 0.103 mol) and sodium carbonate (5eq, 25.92 g, 0.245 mol) were stirred rapidly in 4000 mL water. Groundterephthaloyl chloride was added portionwise at room temperature. Afterstirring for 72 hours, the solution was poured onto 10% HCl. The solidswere collected by filtration and washed with water to give 16.6g (83%yield) of a white powder. An impurity in this product isN-(4-carboxybenzoyl)4-aminobenzoic acid, which is the monoadditionadduct (less than 3%). ¹ H NMR (200 MHz. DMSO-d₆) δ10.74 (2 H, s),8.15-7.90 (12 H, m), 3.4 (2H, br s); IR (nujol) 3360, 1690, 1660, 1610cm⁻¹.

N-(4-carboxyaniline)-N'-(4-Percarboxyaniline)terephthalate (CAPAT)

The title peracid is obtained fromN,N'-di(4-carboxyaniline)terephthalate using the procedure described forCBPBPIP.

EXAMPLE 11 N,N'-Terephthaloyl-(6-aminocaproic acid-6-aminoperoxycaproicacid) (TPACAP)

N,N'-Terephthaloyl-di(6-aminocaproic acid) * is dissolved in sulfuricacid (3.065 mL H₂ SO₄ per gram of carboxylic acid), cooled to 0° C. andtreated with two molar equivalents of 70% hydrogen peroxide. Thismixture is stirred for one hour at room temperature and then poured ontoa large volume of ice water. The precipitated peracid is filtered andwashed until its pH is 4.5-5.0. IR of a 50% active sample exhibitedabsorption at 3320, 1760, 1740, 1710, 1630, 1540 and 1500 cm. HPLCanalysis was conducted for samples with activities of 95%, 87% and 67%.The percentage of diperacid, monoperacid, and dicarboxylic acid was 91,8, 1 (95% active), 82, 12, 5 (87% active) and 38, 49, 10 (67% active),respectively. Extrapolation of these values to a sample with 47%activity gave 0% diperacid, 79% monoperacid and 16% dicarboxylic acid.

EXAMPLE 12

The bleaching performance of a typical amido peroxyacid according to theinvention, i.e. TPACAP, as described in Example 11, was evaluated forremoval of tea (BC-1) stains. Typically the cotton test pieces (3"×4")were stained with the appropriate stain and washed in a Terg-o-tometerfor 15 minutes at 33° C. in a 500 mL aqueous wash solution at pH 8.0.Dosage of the amido peroxyacid was at 5 and 10 ppm active oxygen.

Stain bleaching was measured reflectometrically using a ColorgardSystem/05 Reflectometer. Bleaching was indicated by an increase inreflectance, reported as ΔΔR. In general a ΔΔR of one unit isperceivable in a paired comparison while ΔΔR of two units is perceivablemonadically. In reporting the reflectance change, the change inreflectance caused by general detergency has been accounted for. ThusΔΔR can actually be expressed as:

    ΔΔR=[ΔR peracid+detergent]-Δdetergent

where ΔR is the reflectance difference of the stained fabric after andbefore washing.

                  TABLE                                                           ______________________________________                                        Bleach Performance of TPCAP as Mono and Diperacid                                    10 ppm (active oxygen)                                                                       5 ppm (active oxygen)                                   ______________________________________                                        Diperacid.sup.1                                                                        4.8              4.4                                                 Monoperacid.sup.2                                                                      7.2              5.5                                                 ______________________________________                                         .sup.1 90% di, 10% mono (94% active)                                          .sup.2 100% mono (47% active)                                            

Based on the results as seen in the Table, the TPCAP mono-peracidbleached better than the diperacid.

The foregoing description and examples illustrate selected embodimentsof the present invention. In light thereof, various modifications willbe suggested to one skilled in the art, all of which are within thespirit and purview of this invention.

What is claimed is:
 1. A method for bleaching a substrate comprisingapplying to said substrate an effective amount to remove stain of anamido peroxyacid having the structure: ##STR7## wherein: R is selectedfrom the group consisting of C₁ -C₁₂ alkylene, C₅ -C₁₂ cycloalkylene, C₆-C₁₂ arylene and radical combinations thereof;R¹ and R² areindependently selected from the group consisting of H, C₁ -C₁₆ alkyl andC₆ -C₁₂ aryl radicals and a radical that can form a C₃ -C₁₂ ringtogether with R³ and both nitrogens; R³ is selected from the groupconsisting of C₁ -C₁₂ alkylene, C₅ -C₁₂ cycloalkylene and C₆ -C₁₂arylene radicals; n and n' each are an integer chosen such that the sumthereof is 1; m and m' each are an integer chosen such that the sumthereof is 1; and M is selected from the group consisting of H, alkalimetal, alkaline earth metal, ammonium, alkanolammonium cations andradicals and combinations thereof.
 2. A method according to claim 1wherein the amido peroxyacid has a structure selected from the groupconsisting of: ##STR8## wherein: R¹, R² and R³ are defined in the samemanner as that for formula (I) and z is an integer from 1 to
 20. 3. Amethod according to claim 2 wherein (IV) has the formula: ##STR9##
 4. Amethod according to claim 1 wherein the amido peroxyacid isN-(4-carboxybenzoyl)-N'-(4-percarboxy benzoyl)-1,4-butanediamine.
 5. Amethod according to claim 1 wherein the amido peroxyacid isN-(4-carboxybenzoyl)-N'-(4-percarboxybenzoyl)-1,2-phenylenediamine.
 6. Amethod according to claim 1 wherein the amido peroxyacid isN,N'-succinoyl-(4-carboxyaniline)(4-percarboxy)aniline.
 7. A methodaccording to claim 1 wherein the amido peroxyacid isN-(4-carboxybenzoyl)-N'-(4-percarboxybenzoyl)ethylenediamine.
 8. Amethod according to claim 1 wherein the amido peroxyacid isN-(4-carboxybenzoyl)-N'-(4-percarboxybenzoyl)piperazine.
 9. A methodaccording to claim 1 wherein the amido peroxyacid isN-(4-carboxybenzoyl)-N'-(4-percarboxybenzoyl)-1,4-diaminocyclohexane.10. A method according to claim 1 wherein the amido peroxyacid isN-(4-carboxybenzoyl)-N'-(4-percarboxybenzoyl)-1,4-phenylenediamine. 11.A method according to claim 1 wherein the amido peroxyacid isN-(carboxyadipoyl)-N'-(percarboxyadipoyl)phenylenediamine.
 12. A methodaccording to claim 1 wherein the amido peroxyacid isN-(carboxyadipoyl)-N'-(percarboxyadipoyl)ethylenediamine.
 13. A methodaccording to claim 1 wherein the amido peroxyacid isN-(4-carboxyaniline)-N'-(4-percarboxyaniline) terephthalate.
 14. Ableaching composition comprising:(i) from about 0.01 to about 50% of anamido peroxyacid having the structure: ##STR10## wherein: R is selectedfrom the group consisting of C₁ -C₁₂ alkylene, C₅ -C₁₂ cycloalkylene, C₆-C₁₂ arylene and radical combinations thereof; R¹ and R² areindependently selected from the group consisting of H, C_(1-C) ₁₆ alkyland C₆ -C₁₂ aryl radicals and a radical that can form a C₃ -C₁₂ ringtogether with R³ and both nitrogens; R³ is selected from the groupconsisting of C₁ -C₁₂ alkylene, C₅ -C₁₂ cycloalkylene and C₆ -C₁₂arylene radicals; n and n' each are an integer chosen such that the sumthereof is 1; m and m' each are an integer chosen such that the sumthereof is 1; and M is selected from the group consisting of H, alkalimetal, alkaline earth metal, ammonium, alkanolammonium cations andradicals and combinations thereof, (ii) from about 0.5 to about 50% of asurfactant.
 15. A bleaching composition according to claim 14 whereinthe peroxyacid is present in an amount from about 0.1 to about 30% byweight.
 16. A bleaching composition according to claim 14 wherein theamido peroxyacid has a structure selected from the group consisting of:##STR11## wherein: R¹, R² and R³ are defined in the same manner as thatfor formula (I) and z is an integer from 1 to
 20. 17. A bleachingcomposition according to claim 16 wherein the amido peroxyacid has theformula: ##STR12##